methyl (E)-2-oxo-4-(o-tolyl)but-3-enoate | 1225465-11-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: methyl (E)-2-oxo-4-(o-tolyl)but-3-enoate
• CAS: 1225465-11-1
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: OKORABORNHNVPD-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.75
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl (E)-2-oxo-4-(o-tolyl)but-3-enoate 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 methyl (E)-2-acetoxy-4-(o-tolyl)but-3-enoate
  参考文献：
  名称：

  钯催化不对称烯丙基胺合成手性α，β-不饱和γ-氨基酯

  摘要：

  已经开发了Pd催化的4-取代的2-乙酰氧基丁-3-烯酸酯与胺的不对称烯丙基胺化，用于手性α，β-不饱和γ-氨基酯的区域特异性合成。可以以高达98％的收率和99％ee的产率获得所需的手性胺化产物，并且可以方便地将其转化为手性γ-氨基酸/醇衍生物和手性γ-内酰胺，然后可以对其进行几种类型的合成手性药物和候选药物。手性γ-氨基酯的优先形成可能归因于烯丙基底物右侧的庞大取代基。这项工作为合成手性α，β-不饱和γ-氨基酯及其衍生物提供了有效的策略。

  DOI：

  10.1021/acs.orglett.7b01904
• 作为产物：
  描述：

  1-(二甲氧基甲基)-2-甲基苯 在 三氟化硼乙醚 、 silica gel 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 27.0h， 生成 methyl (E)-2-oxo-4-(o-tolyl)but-3-enoate
  参考文献：
  名称：

  Efficient Enantioselective Synthesis of Dihydropyrans Using a Chiral N,N′-Dioxide as Organocatalyst

  摘要：

  The bifunctional organocatalyst C3 N,N'-dioxide has been successfully applied to the asymmetric cascade Michael/hemiacetalization reaction of alpha-substituted cyano ketones and beta,gamma-unsaturated alpha-ketoesters for the synthesis of multifunctionalized chiral dihydropyrans. The corresponding products were obtained in excellent yields (up to 99%) with high to excellent enantioselectivities (up to 99% ee).

  DOI：

  10.1021/ol400894j

文献信息

• Unexpected Cascade Reactions of <i>Ortho</i> ‐Hydroxyenaminones and β,γ‐Unsaturated α‐Ketoesters to Access Hydrogenated Benzoxazolepolycycles and Pyrrole−Phenol Atropisomers
  作者：Xuguan Bai、Lele Wang、Ziying Zhang、Kuan Zhang、Zhanwei Bu、Yufeng Wu、Wenjing Zhang、Qilin Wang

  DOI：10.1002/adsc.201900950

  日期：2019.11.5

  BF3 ⋅ OEt2‐catalyzed Michael addition/cyclization/dehydration sequence of ortho‐hydroxyenaminones with aromatic or aliphatic aldehyde‐derived β,γ‐unsaturated α‐ketoesters has been achieved to afford a wide range of fused hydrogenated benzoxazole polycycles in 67–95% yields in a highly diastereoselective manner. When isatin‐derived β,γ‐unsaturated α‐ketoesters were employed as substrates, completely different reactivities

  已实现了出乎意料的BF 3  OEt 2催化邻羟基烯酮与芳香族或脂族醛衍生的β，γ-不饱和α-酮酸酯的迈克尔加成/环化/脱水序列，从而在67个范围内提供了多种熔融氢化苯并恶唑多环–95％的非对映选择性很高。当使用由异黄素衍生的β，γ-不饱和α-酮酸酯作为底物时，观察到完全不同的反应性，从而提供了一系列带有氧吲哚取代的N-C轴向手性吡咯-苯酚主链的新型阻转异构体，收率高达97％。此外，进行DFT计算以考虑可能的反应途径和立体化学。
• Chiral<i>N</i>,<i>N′</i>-Dioxide-Yttrium Triflate Complexes-Catalyzed Asymmetric Aldol Cyclization of α-Keto Esters with α-Isothiocyanato Imide
  作者：Xiaohu Zhao、Mingsheng Xie、Xiaohua Liu、Yulong Zhang、Xiao Xiao、Lili Lin、Xiaoming Feng

  DOI：10.1002/adsc.201300593

  日期：2013.11.11

  AbstractA highly effective aldol cyclization of α‐isothiocyanato imide to both β,γ‐unsaturated α‐keto esters and aryl‐substituted α‐keto esters has been developed. A chiral N,N′‐dioxide–yttrium triflate complex was used as the catalyst. A series of cyclic thiocarbamates bearing chiral quaternary stereocenters was synthesized in good to high yields, excellent diastereo‐ (up to 25:1 dr) and enantioselectivities (up to 99 % ee). In addition, the reaction could be carried out on a gram‐scale, and other functionalized derivatives are also conveniently transformed. Interestingly, a discrepancy of diastereoselection was observed between the reactions of β,γ‐unsaturated α‐keto esters and aryl‐substituted α‐keto esters. Moreover, a substrate dependency of non‐linear effects was observed in this reaction. On the basis of the experimental results and the absolute configuration of the products, possible catalytic models have been proposed to explain the origin of the asymmetric process.magnified image